US20170246621A1 - Novel imines with tunable nucleophilicity and steric properties through metal coordination: applications as ligands and metalloorganocatalysts - Google Patents
Novel imines with tunable nucleophilicity and steric properties through metal coordination: applications as ligands and metalloorganocatalysts Download PDFInfo
- Publication number
- US20170246621A1 US20170246621A1 US15/510,119 US201515510119A US2017246621A1 US 20170246621 A1 US20170246621 A1 US 20170246621A1 US 201515510119 A US201515510119 A US 201515510119A US 2017246621 A1 US2017246621 A1 US 2017246621A1
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- US
- United States
- Prior art keywords
- alkyl
- groups
- aryl
- aralkyl
- hydrogen atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003446 ligand Substances 0.000 title claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 28
- 150000002466 imines Chemical class 0.000 title description 9
- -1 phospho-amino Chemical group 0.000 claims abstract description 45
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 66
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 64
- 239000000203 mixture Substances 0.000 claims description 51
- 239000001257 hydrogen Substances 0.000 claims description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 150000002431 hydrogen Chemical class 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 125000000623 heterocyclic group Chemical group 0.000 claims description 12
- 150000004678 hydrides Chemical group 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- 150000002815 nickel Chemical class 0.000 claims description 10
- 229910001453 nickel ion Inorganic materials 0.000 claims description 10
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims description 8
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 45
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 43
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 41
- 238000006243 chemical reaction Methods 0.000 abstract description 37
- 238000000034 method Methods 0.000 abstract description 33
- 150000001299 aldehydes Chemical class 0.000 abstract description 20
- 239000001569 carbon dioxide Substances 0.000 abstract description 14
- 150000001298 alcohols Chemical class 0.000 abstract description 12
- 150000001408 amides Chemical class 0.000 abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 150000005676 cyclic carbonates Chemical class 0.000 abstract description 6
- 238000006352 cycloaddition reaction Methods 0.000 abstract description 6
- 238000006692 trifluoromethylation reaction Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 150000003333 secondary alcohols Chemical class 0.000 abstract description 3
- 150000002118 epoxides Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 60
- 239000003607 modifier Substances 0.000 description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 32
- 125000003118 aryl group Chemical group 0.000 description 31
- 229910052799 carbon Inorganic materials 0.000 description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 18
- 125000004429 atom Chemical group 0.000 description 17
- 0 [1*]P([2*])NC1=CC([5*])=CC([3h]c([3*])[4*])=N1 Chemical compound [1*]P([2*])NC1=CC([5*])=CC([3h]c([3*])[4*])=N1 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 13
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 12
- 125000004093 cyano group Chemical group *C#N 0.000 description 12
- 150000004820 halides Chemical group 0.000 description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 12
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 11
- 125000004122 cyclic group Chemical group 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 125000006413 ring segment Chemical group 0.000 description 8
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- 125000002015 acyclic group Chemical group 0.000 description 7
- 125000000304 alkynyl group Chemical group 0.000 description 7
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical group C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 7
- 238000006459 hydrosilylation reaction Methods 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- 210000000080 chela (arthropods) Anatomy 0.000 description 6
- 150000002924 oxiranes Chemical class 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910018502 Ni—H Inorganic materials 0.000 description 5
- 125000002252 acyl group Chemical group 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 238000000844 transformation Methods 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 235000019445 benzyl alcohol Nutrition 0.000 description 4
- 229960004217 benzyl alcohol Drugs 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000003282 alkyl amino group Chemical group 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000003818 flash chromatography Methods 0.000 description 3
- 125000000879 imine group Chemical group 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- 238000010626 work up procedure Methods 0.000 description 3
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 description 2
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- DXXWOLSSAAMLLL-UHFFFAOYSA-N C1=CC=C(C2CO2)C=C1.O=C1OCC(C2=CC=CC=C2)O1.O=C=O.[H][Ni]12CNC3=CC=CC(=N[PH]1(C(C)(C)C)C(C)(C)C)N32 Chemical compound C1=CC=C(C2CO2)C=C1.O=C1OCC(C2=CC=CC=C2)O1.O=C=O.[H][Ni]12CNC3=CC=CC(=N[PH]1(C(C)(C)C)C(C)(C)C)N32 DXXWOLSSAAMLLL-UHFFFAOYSA-N 0.000 description 2
- 125000006519 CCH3 Chemical group 0.000 description 2
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ZMXDDKWLCZADIW-YYWVXINBSA-N N,N-dimethylformamide-d7 Chemical compound [2H]C(=O)N(C([2H])([2H])[2H])C([2H])([2H])[2H] ZMXDDKWLCZADIW-YYWVXINBSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- KVFDZFBHBWTVID-UHFFFAOYSA-N O=CC1CCCCC1 Chemical compound O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 125000005277 alkyl imino group Chemical group 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000001769 aryl amino group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229940052810 complex b Drugs 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 238000003419 tautomerization reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 2
- MWKJTNBSKNUMFN-UHFFFAOYSA-N trifluoromethyltrimethylsilane Chemical compound C[Si](C)(C)C(F)(F)F MWKJTNBSKNUMFN-UHFFFAOYSA-N 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- FMXHBUBTHCBSSW-UHFFFAOYSA-N C.C.C1=CC=C([SiH2]C2=CC=CC=C2)C=C1.O=C=O Chemical compound C.C.C1=CC=C([SiH2]C2=CC=CC=C2)C=C1.O=C=O FMXHBUBTHCBSSW-UHFFFAOYSA-N 0.000 description 1
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
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Definitions
- the present invention relates generally to the field of chemistry and catalysis. More particularly, it relates to phospho-amino pincer-type ligands, metal complexes thereof, and catalytic methods comprising such metal complexes.
- organocatalysts are small organic molecules containing no metal atoms that accelerate chemical reactions typically via nucleophilic covalent- or hydrogen bonding activations, and their activity and selectivity can also be tuned by varying the steric and/or electronic factors of the substituent groups.
- PN 3 -pincer ligands are provided, with corresponding intermediates, and metal complexes thereof. These PN 3 -pincer complexes have been found to convert carbon dioxide into methanol.
- a complex in one embodiment, includes a ligand and a metal or metal ion, M, wherein the ligand is a compound according to formula (I), or a deprotonated version thereof, and the ligand is associated with the metal or metal ion, M,
- R 1 and R 2 are each independently alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- R 3 , and R 4 are each independently alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- R 5 is a hydrogen atom or an alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- each Z independently, is CR 6 , N or P;
- R 6 is a hydrogen atom or an alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- T is a N, NR 7 , CR 8 , or CR 9 R 10 ;
- R 7 , R 8 , R 9 and R 10 are each independently a hydrogen, alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- Q is P or N
- T and Q together, form a 5 or 6 membered heterocyclic ring; wherein the heterocyclic ring can optionally be substituted with one or more heteroatoms and or one or more sites of the heterocyclic ring are substituted with one or more alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups, and optionally wherein the heterocyclic ring can have a fused ring attached thereto, provided when T and Q form a 5 or 6 membered heterocyclic ring, R 3 and R 4 are not present;
- M is nickel (Ni) or a nickel ion or salt
- X is a halide or a hydrogen atom associated with M or the complex.
- R 1 , R 2 , R 3 , and R 4 are each independently alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- R 5 is a hydrogen atom or an alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- each Z independently, is CR 6 , N or P;
- R 6 is a hydrogen atom or an alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- D is NR 7 or CR 9 R 10 ;
- R 7 , R 9 and R 10 are each independently a hydrogen, alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- M is a nickel (Ni) or a nickel ion or salt
- X is a halide or a hydrogen atom.
- D is NR 7 .
- composition of formula (III) is provided as:
- R 1 , R 2 , R 3 , and R 4 are each independently alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- R 5 is a hydrogen atom or an alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- each Z independently, is CR 6 , N or P;
- R 6 is a hydrogen atom or an alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- R 7 is a hydrogen, alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- M is nickel (Ni), a nickel ion or nickel salt
- X is a halide or a hydrogen atom
- R 1 , R 2 , R 3 , and R 4 are each an alkyl (C2-10) , each Z is CH, T, if present, is N or NR 7 and R 5 is a hydrogen atom.
- R 1 , R 2 , R 3 , and R 4 are each a C 4 alkyl and T, if present, is NR 7 , wherein R 7 is a methyl group or a hydrogen atom (hydride).
- X is a hydrogen atom (a hydride).
- X is a halide
- the present disclosure provides phospho-amino ligands and methods which include the use of the ligands and their complexes described herein to catalyze reactions between one or more reactants.
- the phospho-amino ligands described herein e.g. Formulae (I) through (III)
- These syntheses provide the basis for the useful and unexpected nature of the organocatalysts described herein.
- the present embodiments provide advantages such as that the Ni—PN3P complexes have similar reactivities as those of N-heterocyclic carbenes, the production cost is 90% lower than that of carbenes and more specifically, the Ni—PN3P complexes show more efficient reactivity in catalyzing reduction of CO 2 to methanol that known complexes.
- FIG. 1 depicts the molecular structure of complex 1 of Scheme 6. Ni1-N1 1.904, C1-N2 1.392, P2-N2 1.697, C5-N3 1.322, P1-N3 1.661, Ni1-Cl1 2.188, N1-Ni1-Cl1 178.12.
- FIG. 2 depicts the molecular structure of complex 2 of Scheme 6. Ni1-N2 1.900, C1-N1 1.380, P1-N1 1.702, C5-N3 1.334, P2-N3 1.673, Ni1-H 1.446, N2-Ni1-H 179.80.
- a new class of pincer-type ligands including those having a disubstituted-phosphinoamino (NH-PR 2 ) arm.
- Metal complexes of such ligands are also provided, including complexes that may be used as catalysts for a variety of transformations, including, for example, conversion of carbon dioxide to methanol.
- the resulting complex can undergo dearomatization after the elimination of H—X.
- Nickel PN 3 P-pincer complex 2 is an efficient organocatalyst that catalyzed the reduction of CO 2 with silane with 4500 TON and 125 h ⁇ 1 TOF, much better than N-heterocyclic carbene (Scheme 2a). It was found that by replacing the chloride ligand to a more a-donating hydride ligand on the nickel PN 3 P-pincer complex, the nucleophilicity of the imine N was greatly enhanced to the extent that its reactivity towards carbonyl compounds was higher. The imine N could also activate aldehyde functionality for efficient selective reduction to the corresponding primary alcohols in excellent yields (Scheme 2b).
- Nickel PN 3 P-pincer complex 2 served as an organocatalyst like N-heterocyclic carbene to catalyze the trifluoromethylation reaction of benzaldehyde to provide CF 3 -substituted alcohols in good yield (Scheme 3).
- Nickel PN 3 P-pincer complex 2 could also be used as an organocatalyst like guanidine to catalyze the cycloaddition of CO 2 to epoxide (Scheme 4).
- N-heterocyclic carbene based ruthenium complexes were developed as highly active catalysts for the direct amide synthesis from alcohols and amines. 17 Nickel PN 3 P-pincer complex 2 was used as an efficient ligand like N-heterocyclic carbene for the ruthenium-catalyzed direct amide synthesis from alcohols and amines (Scheme 5).
- a suitable a ligand and a metal or metal ion, M wherein the ligand is a compound according to formula (I), or a deprotonated version thereof, and the ligand is associated with the metal or metal ion, M,
- R 1 and R 2 are each independently alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- R 3 , and R 4 are each independently alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- R 5 is a hydrogen atom or an alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- each Z independently, is CR 6 , N or P;
- R 6 is a hydrogen atom or an alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- T is a N, NR S , CR 8 , or CR 9 R 10 ;
- R 7 , R 8 , R 9 and R 10 are each independently a hydrogen, alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- Q is P or N
- T and Q together, form a 5 or 6 membered heterocyclic ring; wherein the heterocyclic ring can optionally be substituted with one or more heteroatoms and or one or more sites of the heterocyclic ring are substituted with one or more alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups, and optionally wherein the heterocyclic ring can have a fused ring attached thereto, provided when T and Q form a 5 or 6 membered heterocyclic ring, R 3 and R 4 are not present;
- M is nickel (Ni), a nickel ion or a nickel salt
- X is a halide or a hydrogen atom associated with M or the complex.
- Halides include, for example, chloride, bromide, iodide, or fluoride.
- metal or metal ion “M” can be covalent, ionic, van der Waals type interactions, complexation interactions or other types of interactions where the metal (M). It should be understood that there is an association with the metal or metal ion and one or more of the nitrogen of the pyridine ring, the dearomatized N of the pyridine ring, a “P”, a “T”, an NH, an imine nitrogen, or “Q” of the ligands described herein.
- the stereochemistry of “X” associated with the metal or metal ion “M” is not limited to a planar structure but is merely depicted this way for convenience.
- Selected structures include, for example, PN 3 P-pincer nickel (Ni) complexes 1 through 3, which are useful for dehydrogenation of formic acid are depicted below. Further details regarding different embodiments are provided throughout this disclosure.
- the disclosure provides compounds of formulae (I) through (III) as well as the ligands for complexes noted throughout.
- the present disclosure also provides metal complexes of this novel class of ligands.
- Such complexes may be used to facilitate a variety of organic transformations, including conversion of carbon dioxide to methanol, conversion of aldehydes into alcohols, conversion of aldehydes in the presence of a trifluoromethylation agent into trifluorinated secondary alcohols, cycloaddition of carbon dioxide to an epoxide to provide cyclic carbonates and preparation of an amide from the combination of an alcohol and an amine.
- nickel complexes of ligands can be made, and optionally deprotonated, to provide a dearomatized pyridine moiety and an imine arm.
- Nickel complexes of ligands 1, 2 and 3 can catalyze, for example, the conversion of aldehydes to alcohols (Tables 1 and 2) or carbon dioxide to methanol (Table 3).
- hydrogen means —H; “hydroxy” means —OH; “oxo” means ⁇ O; “halo” means independently —F, —Cl, —Br or —I; “amino” means —NH 2 (see below for definitions of groups containing the term amino, e.g., alkylamino); “hydroxyamino” means —NHOH; “nitro” means —NO 2 ; imino means ⁇ NH (see below for definitions of groups containing the term imino, e.g., alkylimino); “cyano” means —CN; “isocyanate” means —N ⁇ C ⁇ O; “azido” means —N 3 ; in a monovalent context “phosphate” means —OP(O)(OH) 2 or a deprotonated form thereof; in a divalent context “phosphate” means —OP(O)(OH)O— or a deprotonated form
- the symbol “ ”, when drawn perpendicularly across a bond indicates a point of attachment of the group. It is noted that the point of attachment is typically only identified in this manner for larger groups in order to assist the reader in rapidly and unambiguously identifying a point of attachment.
- the symbol “ ” means a single bond where the group attached to the thick end of the wedge is “out of the page.”
- the symbol “ ” means a single bond where the group attached to the thick end of the wedge is “into the page”.
- the symbol “ ” means a single bond where the conformation (e.g., either R or S) or the geometry is undefined (e.g., either E or Z).
- R may replace any hydrogen atom attached to any of the ring atoms, including a depicted, implied, or expressly defined hydrogen, so long as a stable structure is formed.
- R may replace any hydrogen atom attached to any of the ring atoms, including a depicted, implied, or expressly defined hydrogen, so long as a stable structure is formed.
- R may replace any hydrogen attached to any of the ring atoms of either of the fused rings unless specified otherwise.
- Replaceable hydrogens include depicted hydrogens (e.g., the hydrogen attached to the nitrogen in the formula above), implied hydrogens (e.g., a hydrogen of the formula above that is not shown but understood to be present), expressly defined hydrogens, and optional hydrogens whose presence depends on the identity of a ring atom (e.g., a hydrogen attached to group X, when X equals —CH—), so long as a stable structure is formed.
- R may reside on either the 5-membered or the 6-membered ring of the fused ring system.
- the subscript letter “y” immediately following the group “R” enclosed in parentheses represents a numeric variable. Unless specified otherwise, this variable can be 0, 1, 2, or any integer greater than 2, only limited by the maximum number of replaceable hydrogen atoms of the ring or ring system.
- (Cn) defines the exact number (n) of carbon atoms in the group/class.
- (C ⁇ n) defines the maximum number (n) of carbon atoms that can be in the group/class, with the minimum number as small as possible for the group in question, e.g., it is understood that the minimum number of carbon atoms in the group “alkenyl (C ⁇ 8) ” or the class “alkene (C ⁇ 8) ” is two.
- alkoxy (C ⁇ 10) designates those alkoxy groups having from 1 to 10 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, or any range derivable therein (e.g., 3 to 10 carbon atoms).
- Cn-n′ defines both the minimum (n) and maximum number (n′) of carbon atoms in the group.
- alkyl (C2-10) designates those alkyl groups having from 2 to 10 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, or 10, or any range derivable therein (e.g., 3 to 10 carbon atoms)).
- saturated means the compound or group so modified has no carbon-carbon double and no carbon-carbon triple bonds, except as noted below.
- the term does not preclude carbon-heteroatom multiple bonds, for example a carbon oxygen double bond or a carbon nitrogen double bond. Moreover, it does not preclude a carbon-carbon double bond that may occur as part of keto-enol tautomerism or imine/enamine tautomerism.
- aliphatic when used without the “substituted” modifier signifies that the compound/group so modified is an acyclic or cyclic, but non-aromatic hydrocarbon compound or group.
- the carbon atoms can be joined together in straight chains, branched chains, or non-aromatic rings (alicyclic).
- Aliphatic compounds/groups can be saturated, that is joined by single bonds (alkanes/alkyl), or unsaturated, with one or more double bonds (alkenes/alkenyl) or with one or more triple bonds (alkynes/alkynyl).
- one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH 2 , —NO 2 , —CO 2 H, —CO 2 CH 3 , —CN, —SH, —OCH 3 , —OCH 2 CH 3 , —C(O)CH 3 , —N(CH 3 ) 2 , —C(O)NH 2 or —OC(O)CH 3 .
- alkyl when used without the “substituted” modifier refers to a monovalent saturated aliphatic group with a carbon atom as the point of attachment, a linear or branched, cyclo, cyclic or acyclic structure, and no atoms other than carbon and hydrogen.
- cycloalkyl is a subset of alkyl.
- the groups —CH 3 (Me), —CH 2 CH 3 (Et), —CH 2 CH 2 CH 3 (n-Pr), —CH(CH 3 ) 2 (iso-Pr), —CH(CH 2 ) 2 (cyclopropyl), —CH 2 CH 2 CH 2 CH 3 (n-Bu), —CH(CH 3 )CH 2 CH 3 (sec-butyl), —CH 2 CH(CH 3 ) 2 (iso-butyl), —C(CH 3 ) 3 (tert-butyl), —CH 2 C(CH 3 ) 3 (neo-pentyl), cyclobutyl, cyclopentyl, cyclohexyl, and cyclohexylmethyl are non-limiting examples of alkyl groups.
- alkanediyl when used without the “substituted” modifier refers to a divalent saturated aliphatic group, with one or two saturated carbon atom(s) as the point(s) of attachment, a linear or branched, cyclo, cyclic or acyclic structure, no carbon-carbon double or triple bonds, and no atoms other than carbon and hydrogen.
- alkanediyl groups are non-limiting examples of alkanediyl groups.
- alkylidene when used without the “substituted” modifier refers to the divalent group ⁇ CRR′ in which R and R′ are independently hydrogen, alkyl, or R and R′ are taken together to represent an alkanediyl having at least two carbon atoms.
- alkylidene groups include: ⁇ CH 2 , ⁇ CH(CH 2 CH 3 ), and ⁇ C(CH 3 ) 2 .
- the following groups are non-limiting examples of substituted alkyl groups: —CH 2 OH, —CH 2 Cl, —CF 3 , —CH 2 CN, —CH 2 C(O)OH, —CH 2 C(O)OCH 3 , —CH 2 C(O)NH 2 , —CH 2 C(O)CH 3 , —CH 2 OCH 3 , —CH 2 OC(O)CH 3 , —CH 2 NH 2 , —CH 2 N(CH 3 ) 2 , and —CH 2 CH 2 Cl.
- fluoroalkyl is a subset of substituted alkyl, in which one or more hydrogen has been substituted with a fluoro group and no other atoms aside from carbon, hydrogen and fluorine are present.
- the groups, —CH 2 F, —CF 3 , and —CH 2 CF 3 are non-limiting examples of fluoroalkyl groups.
- An “alkane” refers to the compound H—R, wherein R is alkyl.
- alkenyl when used without the “substituted” modifier refers to an monovalent unsaturated aliphatic group with a carbon atom as the point of attachment, a linear or branched, cyclo, cyclic or acyclic structure, at least one nonaromatic carbon-carbon double bond, no carbon-carbon triple bonds, and no atoms other than carbon and hydrogen.
- alkenyl groups include: —CH ⁇ CH 2 (vinyl), —CH ⁇ CHCH 3 , —CH ⁇ CHCH 2 CH 3 , —CH 2 CH ⁇ CH 2 (allyl), —CH 2 CH ⁇ CHCH 3 , and —CH ⁇ CH—C 6 H 5 .
- alkenediyl when used without the “substituted” modifier refers to a divalent unsaturated aliphatic group, with two carbon atoms as points of attachment, a linear or branched, cyclo, cyclic or acyclic structure, at least one nonaromatic carbon-carbon double bond, no carbon-carbon triple bonds, and no atoms other than carbon and hydrogen.
- the groups —CH ⁇ CH—, —CH ⁇ C(CH 3 )CH 2 —, —CH ⁇ CHCH 2 —, and
- alkenediyl groups are non-limiting examples of alkenediyl groups.
- substituents refers to the compound H—R, wherein R is alkenyl.
- alkynyl when used without the “substituted” modifier refers to an monovalent unsaturated aliphatic group with a carbon atom as the point of attachment, a linear or branched, cyclo, cyclic or acyclic structure, at least one carbon-carbon triple bond, and no atoms other than carbon and hydrogen.
- alkynyl does not preclude the presence of one or more non-aromatic carbon-carbon double bonds.
- the groups, —C ⁇ CH, —C ⁇ CCH 3 , and —CH 2 C ⁇ CCH 3 are non-limiting examples of alkynyl groups.
- alkynediyl when used without the “substituted” modifier refers to a divalent unsaturated aliphatic group, with two carbon atoms as points of attachment, a linear or branched, cyclo, cyclic or acyclic structure, at least one carbon-carbon triple bond, and no atoms other than carbon and hydrogen.
- aryl when used without the “substituted” modifier refers to a monovalent unsaturated aromatic group with an aromatic carbon atom as the point of attachment, said carbon atom forming part of a one or more six-membered aromatic ring structure, wherein the ring atoms are all carbon, and wherein the group consists of no atoms other than carbon and hydrogen. If more than one ring is present, the rings may be fused or not fused. As used herein, the term does not preclude the presence of one or more alkyl group (carbon number limitation permitting) attached to the first aromatic ring or any additional aromatic ring present.
- Non-limiting examples of aryl groups include phenyl (Ph), methylphenyl, (dimethyl)phenyl, —C 6 H 4 CH 2 CH 3 (ethylphenyl), naphthyl, and the monovalent group derived from biphenyl.
- aromaticiyl when used without the “substituted” modifier refers to a divalent aromatic group, with two aromatic carbon atoms as points of attachment, said carbon atoms forming part of one or more six-membered aromatic ring structure(s) wherein the ring atoms are all carbon, and wherein the monovalent group consists of no atoms other than carbon and hydrogen.
- the term does not preclude the presence of one or more alkyl group (carbon number limitation permitting) attached to the first aromatic ring or any additional aromatic ring present. If more than one ring is present, the rings may be fused or unfused.
- alkyl group carbon number limitation permitting
- arenediyl groups include:
- one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH 2 , —NO 2 , —CO 2 H, —CO 2 CH 3 , —CN, —SH, —OCH 3 , —OCH 2 CH 3 , —C(O)CH 3 , —N(CH 3 ) 2 , —C(O)NH 2 or —OC(O)CH 3 .
- An “arene” refers to the compound H—R, wherein R is aryl.
- aralkyl when used without the “substituted” modifier refers to the monovalent group -alkanediyl-aryl, in which the terms alkanediyl and aryl are each used in a manner consistent with the definitions provided above.
- Non-limiting examples of aralkyls are: phenylmethyl (benzyl, Bn) and 2-phenyl-ethyl.
- one or more hydrogen atom from the alkanediyl and/or the aryl has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH 2 , —NO 2 , —CO 2 H, —CO 2 CH 3 , —CN, —SH, —OCH 3 , —OCH 2 CH 3 , —C(O)CH 3 , —N(CH 3 ) 2 , —C(O)NH 2 or —OC(O)CH 3 .
- substituted aralkyls are: (3-chlorophenyl)-methyl, and 2-chloro-2-phenyl-eth-1-yl.
- heteroaryl when used without the “substituted” modifier refers to a monovalent aromatic group with an aromatic carbon atom or nitrogen atom as the point of attachment, said carbon atom or nitrogen atom forming part of an aromatic ring structure wherein at least one of the ring atoms is nitrogen, oxygen or sulfur, and wherein the group consists of no atoms other than carbon, hydrogen, aromatic nitrogen, aromatic oxygen and aromatic sulfur.
- the term does not preclude the presence of one or more alkyl group (carbon number limitation permitting) attached to the aromatic ring or any additional aromatic ring present.
- heteroaryl groups include furanyl, imidazolyl, indolyl, indazolyl (Im), methylpyridyl, oxazolyl, pyridyl, pyrrolyl, pyrimidyl, pyrazinyl, quinolyl, quinazolyl, quinoxalinyl, thienyl, and triazinyl.
- heteroarenediyl when used without the “substituted” modifier refers to an divalent aromatic group, with two aromatic carbon atoms, two aromatic nitrogen atoms, or one aromatic carbon atom and one aromatic nitrogen atom as the two points of attachment, said atoms forming part of one or more aromatic ring structure(s) wherein at least one of the ring atoms is nitrogen, oxygen or sulfur, and wherein the divalent group consists of no atoms other than carbon, hydrogen, aromatic nitrogen, aromatic oxygen and aromatic sulfur.
- the term does not preclude the presence of one or more alkyl group (carbon number limitation permitting) attached to the first aromatic ring or any additional aromatic ring present. If more than one ring is present, the rings may be fused or unfused.
- Non-limiting examples of heteroarenediyl groups include:
- one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH 2 , —NO 2 , —CO 2 H, —CO 2 CH 3 , —CN, —SH, —OCH 3 , —OCH 2 CH 3 , —C(O)CH 3 , —N(CH 3 ) 2 , —C(O)NH 2 or —OC(O)CH 3 .
- acyl when used without the “substituted” modifier refers to the group —C(O)R, in which R is a hydrogen, alkyl, aryl, aralkyl or heteroaryl, as those terms are defined above.
- the groups, —CHO, —C(O)CH 3 (acetyl, Ac), —C(O)CH 2 CH 3 , —C(O)CH 2 CH 2 CH 3 , —C(O)CH(CH 3 ) 2 , —C(O)CH(CH 2 ) 2 , C(O)C 6 H 5 , C(O)C 6 H 4 CH 3 , C(O)CH 2 C 6 H 5 , —C(O)(imidazolyl) are non-limiting examples of acyl groups.
- a “thioacyl” is defined in an analogous manner, except that the oxygen atom of the group —C(O)R has been replaced with a sulfur atom, —C(S)R.
- one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH 2 , —NO 2 , —CO 2 H, —CO 2 CH 3 , —CN, —SH, —OCH 3 , —OCH 2 CH 3 , —C(O)CH 3 , —N(CH 3 ) 2 , —C(O)NH 2 or —OC(O)CH 3 .
- the groups, —C(O)CH 2 CF 3 , —CO 2 H (carboxyl), —CO 2 CH 3 (methylcarboxyl), —CO 2 CH 2 CH 3 , —C(O)NH 2 (carbamoyl), and —CON(CH 3 ) 2 are non-limiting examples of substituted acyl groups.
- alkoxy when used without the “substituted” modifier refers to the group —OR, in which R is an alkyl, as that term is defined above.
- alkoxy groups include: —OCH 3 , —OCH 2 CH 3 , —OCH 2 CH 2 CH 3 , —OCH(CH 3 ) 2 , —OCH(CH 2 ) 2 , —O-cyclopentyl, and —O-cyclohexyl.
- alkenyloxy when used without the “substituted” modifier, refers to groups, defined as —OR, in which R is alkenyl, alkynyl, aryl, aralkyl, heteroaryl, and acyl, respectively.
- alkylthio when used without the “substituted” modifier refers to the group —SR, in which R is an alkyl, as that term is defined above.
- alkylamino when used without the “substituted” modifier refers to the group —NHR, in which R is an alkyl, as that term is defined above.
- alkylamino groups include: —NHCH 3 and —NHCH 2 CH 3 .
- dialkylamino when used without the “substituted” modifier refers to the group —NRR′, in which R and R′ can be the same or different alkyl groups, or R and R′ can be taken together to represent an alkanediyl.
- Non-limiting examples of dialkylamino groups include: —N(CH 3 ) 2 , —N(CH 3 )(CH 2 CH 3 ), and N-pyrrolidinyl.
- dialkylamino groups include: —N(CH 3 ) 2 , —N(CH 3 )(CH 2 CH 3 ), and N-pyrrolidinyl.
- alkoxyamino “alkenylamino”, “alkynylamino”, “arylamino”, “aralkylamino”, “heteroarylamino”, and “alkylsulfonylamino” when used without the “substituted” modifier, refers to groups, defined as —NHR, in which R is alkoxy, alkenyl, alkynyl, aryl, aralkyl, heteroaryl, and alkylsulfonyl, respectively.
- a non-limiting example of an arylamino group is —NHC 6 H 5 .
- a non-limiting example of an amido group is —NHC(O)CH 3 .
- alkylimino when used without the “substituted” modifier refers to the divalent group ⁇ NR, in which R is an alkyl, as that term is defined above.
- the present invention provides a complex comprising a ligand and a metal or metal ion, M, wherein the ligand is a compound according to formula (I), or a deprotonated version thereof, and the ligand is associated with the metal or metal ion, M,
- R 1 and R 2 are each independently alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- R 3 , and R 4 are each independently alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- R 5 is a hydrogen atom or an alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- each Z independently, is CR 6 , N or P;
- R 6 is a hydrogen atom or an alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- T is a N, NR 7 , CR 8 , or CR 9 R 10 ;
- R 7 , R 8 , R 9 and R 10 are each independently a hydrogen, alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- Q is P or N
- T and Q together, form a 5 or 6 membered heterocyclic ring; wherein the heterocyclic ring can optionally be substituted with one or more heteroatoms and or one or more sites of the heterocyclic ring are substituted with one or more alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups, and optionally wherein the heterocyclic ring can have a fused ring attached thereto, provided when T and Q form a 5 or 6 membered heterocyclic ring, R 3 and R 4 are not present;
- M is nickel (Ni), a nickel ion or a nickel salt
- X is a halide or a hydrogen atom associated with M or the complex.
- R 1 , R 2 , R 3 , and R 4 are each independently alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- R 5 is a hydrogen atom or an alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- each Z independently, is CR 6 , N or P;
- R 6 is a hydrogen atom or an alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- D is NR 7 or CR 9 R 10 ; in one aspect, D is NR 7 .
- R 7 , R 9 and R 10 are each independently a hydrogen, alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- M is a nickel (Ni) or a nickel ion or salt
- X is a halide or a hydrogen atom.
- R 1 , R 2 , R 3 , and R 4 are each a alkyl (C2-10) , each Z is CH and R 5 is a hydrogen atom.
- composition comprising formula (III):
- R 1 , R 2 , R 3 , and R 4 are each independently alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- R 5 is a hydrogen atom or an alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- each Z independently, is CR 6 , N or P;
- R 6 is a hydrogen atom or an alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- R 7 is a hydrogen, alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups;
- M is nickel (Ni), a nickel ion or a nickel salt
- X is a halide or a hydrogen atom
- composition of paragraph 20, wherein the amine is an alkylamine comprising NR 20 R 21 R 23 , wherein R 20 , R 21 and R 23 are each independently a hydrogen atom, alkyl (C ⁇ 12) , aryl (C ⁇ 12) , aralkyl (C ⁇ 12) , or a substituted version of any of these groups, wherein one or more of R 20 , R 21 and R 22 can form a ring or an aromatic amine.
- a method to prepare methanol from carbon dioxide comprising the step:
- a method to prepare alcohols from an aldehyde comprising the step:
- a method to trifluoromethylate an aldehyde comprising the step:
- a method to prepare cyclic carbonates from an alkyl or aryl epoxide and carbon dioxide comprising the step:
- complex B was obtained by heating NiCl 2 with ligand A in toluene, a similar procedure to that of its bromide analog by Kirchner. 22,23
- t-BuOK deprotonation afforded the dearomatized pincer nickel complex 1.
- the preparation of Ni—H complex 2 was achieved by oxidative addition of A to bis(1,5-cyclooctadiene)nickel(0) in toluene (Scheme 6). Upon treatment with t-BuOK and methyl iodide in toluene, complex 2 was methylated to afford pincer Ni—H complex 3.
- the ligands and complexes can be prepared by the methods described in U.S. patent Ser. No. 13/528,481, filed on Jun. 6, 2012, entitled “Phospho-amino Pincer-Type Ligands and Catalytic Metal Complexes Thereof”, U.S. Provisional Patent Application No. 61/499,028, filed Jun. 20, 2011, and “Efficient transfer hydrogenation reaction Catalyzed by a dearomatized PN 3 P ruthenium pincer complex under base-free Conditions”, Journal of Organometallic Chemistry, 700 (2012) 202-206, “A sustainable catalytic pyrrole synthesis”, Nature Chemistry Vol. 5, 2013, 140-144 and Z. anorg. allg. Chem. 545 (1987) 83-97, the contents of which are incorporated herein by reference in their entirety.
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Abstract
Description
- This International Application claims priority to U.S. Provisional Patent Application Ser. No. 62/049,022, filed Sep. 11, 2014, entitled “Novel Imines with tunable nucleophilicity and steric properties through metal coordination: Applications as ligands and Metalloorganocatalysts”, the contents of which are incorporated herein in their entirety for all purposes.
- The present invention relates generally to the field of chemistry and catalysis. More particularly, it relates to phospho-amino pincer-type ligands, metal complexes thereof, and catalytic methods comprising such metal complexes.
- Applications of molecular organometallic/coordination complexes as catalysts in organic transformations have been studied, and these reactions typically proceed at the metal atom as the catalytic center whose activity and selectivity are manipulated by modifying the steric and/or electronic properties of the surrounding organic ligands.1,2 On the other hand, organocatalysts are small organic molecules containing no metal atoms that accelerate chemical reactions typically via nucleophilic covalent- or hydrogen bonding activations, and their activity and selectivity can also be tuned by varying the steric and/or electronic factors of the substituent groups.3-7 Since the coordination to a metal center could influence the property of the ligand, it is conceivable that this interaction could in principle be utilized to offer new strategies for the design and modifications of “organocatalysts” through changing the coordinated metal and its spectator ligands. Such an idea, however, has not been comprehensively examined, presumably due to the highly reactive nature of the metal atoms. Nevertheless, the possibility of enhancing the reactivity of the ligand through complexation with a metal is desired. For example, “cooperating” ligands can participate directly in the bond breaking and forming step together with the metal center to activate substrates to achieve metal-ligand cooperative catalysis.8-13
- Therefore, a need exists for the development of novel catalyst systems that overcome one or more of the current disadvantages noted above or expand upon what is currently known.
- In one aspect, PN3-pincer ligands are provided, with corresponding intermediates, and metal complexes thereof. These PN3-pincer complexes have been found to convert carbon dioxide into methanol.
- In one embodiment, a complex is presented that includes a ligand and a metal or metal ion, M, wherein the ligand is a compound according to formula (I), or a deprotonated version thereof, and the ligand is associated with the metal or metal ion, M,
- wherein R1 and R2, are each independently alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- R3, and R4, if present, are each independently alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- R5 is a hydrogen atom or an alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- each Z, independently, is CR6, N or P;
- R6 is a hydrogen atom or an alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- T is a N, NR7, CR8, or CR9R10;
- R7, R8, R9 and R10 are each independently a hydrogen, alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- Q is P or N;
- optionally, wherein T and Q, together, form a 5 or 6 membered heterocyclic ring; wherein the heterocyclic ring can optionally be substituted with one or more heteroatoms and or one or more sites of the heterocyclic ring are substituted with one or more alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups, and optionally wherein the heterocyclic ring can have a fused ring attached thereto, provided when T and Q form a 5 or 6 membered heterocyclic ring, R3 and R4 are not present;
-
- M is nickel (Ni) or a nickel ion or salt; and
- X is a halide or a hydrogen atom associated with M or the complex.
- In another embodiment, a compound of formula (II) is provided as:
- wherein R1, R2, R3, and R4 are each independently alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- R5 is a hydrogen atom or an alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- each Z, independently, is CR6, N or P;
- R6 is a hydrogen atom or an alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- D is NR7 or CR9R10;
- R7, R9 and R10 are each independently a hydrogen, alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- M is a nickel (Ni) or a nickel ion or salt; and
- X is a halide or a hydrogen atom.
- In one aspect, D is NR7.
- In still another embodiment, a composition of formula (III) is provided as:
- wherein R1, R2, R3, and R4 are each independently alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- R5 is a hydrogen atom or an alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- each Z, independently, is CR6, N or P;
- R6 is a hydrogen atom or an alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- R7 is a hydrogen, alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- M is nickel (Ni), a nickel ion or nickel salt;
- X is a halide or a hydrogen atom; and
- a base.
- In one aspect for the various embodiments, R1, R2, R3, and R4 are each an alkyl(C2-10), each Z is CH, T, if present, is N or NR7 and R5 is a hydrogen atom.
- In another aspect for the various embodiments, R1, R2, R3, and R4 are each a C4 alkyl and T, if present, is NR7, wherein R7 is a methyl group or a hydrogen atom (hydride).
- In still yet another aspect for the various embodiments, X is a hydrogen atom (a hydride).
- In yet another aspect for the various embodiments, X is a halide.
- In one aspect, the present disclosure provides phospho-amino ligands and methods which include the use of the ligands and their complexes described herein to catalyze reactions between one or more reactants. For example, the phospho-amino ligands described herein, e.g. Formulae (I) through (III), can be used for the conversion of carbon dioxide into methanol, the conversion of aldehydes into alcohols, the conversion of aldehydes in the presence of a trifluoromethylation agent into trifluorinated secondary alcohols, the cycloaddition of carbon dioxide to an epoxide to provide cyclic carbonates and the preparation of an amide from the combination of an alcohol and an amine. These syntheses provide the basis for the useful and unexpected nature of the organocatalysts described herein.
- The present embodiments provide advantages such as that the Ni—PN3P complexes have similar reactivities as those of N-heterocyclic carbenes, the production cost is 90% lower than that of carbenes and more specifically, the Ni—PN3P complexes show more efficient reactivity in catalyzing reduction of CO2 to methanol that known complexes.
- While multiple embodiments are disclosed, still other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description. As will be apparent, the invention is capable of modifications in various obvious aspects, all without departing from the spirit and scope of the present invention. Accordingly, the detailed descriptions are to be regarded as illustrative in nature and not restrictive.
-
FIG. 1 depicts the molecular structure of complex 1 ofScheme 6. Ni1-N1 1.904, C1-N2 1.392, P2-N2 1.697, C5-N3 1.322, P1-N3 1.661, Ni1-Cl1 2.188, N1-Ni1-Cl1 178.12. -
FIG. 2 depicts the molecular structure of complex 2 ofScheme 6. Ni1-N2 1.900, C1-N1 1.380, P1-N1 1.702, C5-N3 1.334, P2-N3 1.673, Ni1-H 1.446, N2-Ni1-H 179.80. - In certain aspects disclosed herein, there are provided a new class of pincer-type ligands, including those having a disubstituted-phosphinoamino (NH-PR2) arm. Metal complexes of such ligands are also provided, including complexes that may be used as catalysts for a variety of transformations, including, for example, conversion of carbon dioxide to methanol.
- Upon complexation of ligands described herein to a transition metal and treatment of a base, in some embodiments, the resulting complex can undergo dearomatization after the elimination of H—X.
- wherein T, Q and Z are as described herein.
- A new class of compounds with a general structure shown in Scheme la is provided. A series of examples of well-defined nickel PN3P-pincer complexes were prepared (Scheme 1b) and it has been demonstrated that the coordination to the metal center could influence the property of the ligand. Such interactions can be utilized to offer new strategies to design new “metalloorganocatalysts” and ligands. The properties of these compounds can be tuned by modifying the metal center and its spectator ligands, and the substituents in the ligand.
- The unique reactivities of this new class of imine σ-donor catalysts and ligands have been demonstrated in the following reactions.
- Zhang and Ying reported the first N-heterocyclic carbene catalyzed reduction of CO2 with silane under ambient conditions to give methanol with 1840 TON and 25.5 h−1 TOF in 2009.14 Nickel PN3P-pincer complex 2 is an efficient organocatalyst that catalyzed the reduction of CO2 with silane with 4500 TON and 125 h−1 TOF, much better than N-heterocyclic carbene (Scheme 2a). It was found that by replacing the chloride ligand to a more a-donating hydride ligand on the nickel PN3P-pincer complex, the nucleophilicity of the imine N was greatly enhanced to the extent that its reactivity towards carbonyl compounds was higher. The imine N could also activate aldehyde functionality for efficient selective reduction to the corresponding primary alcohols in excellent yields (Scheme 2b).
- In 2005, Song and coworkers reported a novel N-heterocyclic carbene catalyzed trifluoromethylation reaction of benzaldehydes.15 Nickel PN3P-pincer complex 2 served as an organocatalyst like N-heterocyclic carbene to catalyze the trifluoromethylation reaction of benzaldehyde to provide CF3-substituted alcohols in good yield (Scheme 3).
- Sartori and coworkers demonstrated that the synthesis of cyclic carbonates by CO2 insertion into epoxides can be carried out under catalytic conditions by using guanidines.16 Nickel PN3P-pincer complex 2 could also be used as an organocatalyst like guanidine to catalyze the cycloaddition of CO2 to epoxide (Scheme 4).
- N-heterocyclic carbene based ruthenium complexes were developed as highly active catalysts for the direct amide synthesis from alcohols and amines.17 Nickel PN3P-pincer complex 2 was used as an efficient ligand like N-heterocyclic carbene for the ruthenium-catalyzed direct amide synthesis from alcohols and amines (Scheme 5).
- Complexes or compositions disclosed herein can be utilized in the transformations depicted herein. For example, a suitable a ligand and a metal or metal ion, M, wherein the ligand is a compound according to formula (I), or a deprotonated version thereof, and the ligand is associated with the metal or metal ion, M,
- wherein R1 and R2, are each independently alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- R3, and R4, if present, are each independently alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- R5 is a hydrogen atom or an alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- each Z, independently, is CR6, N or P;
- R6 is a hydrogen atom or an alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- T is a N, NRS, CR8, or CR9R10;
- R7, R8, R9 and R10 are each independently a hydrogen, alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- Q is P or N;
- optionally, wherein T and Q, together, form a 5 or 6 membered heterocyclic ring; wherein the heterocyclic ring can optionally be substituted with one or more heteroatoms and or one or more sites of the heterocyclic ring are substituted with one or more alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups, and optionally wherein the heterocyclic ring can have a fused ring attached thereto, provided when T and Q form a 5 or 6 membered heterocyclic ring, R3 and R4 are not present;
-
- M is nickel (Ni), a nickel ion or a nickel salt; and
- X is a halide or a hydrogen atom associated with M or the complex.
- Similarly, complexes or compositions noted herein as formula (II) or (III) can be utilized in the transformations disclosed throughout the specification.
- Halides, as noted herein, include, for example, chloride, bromide, iodide, or fluoride.
- It should be understood that the dative bonds depicted with metal or metal ion “M” can be covalent, ionic, van der Waals type interactions, complexation interactions or other types of interactions where the metal (M). It should be understood that there is an association with the metal or metal ion and one or more of the nitrogen of the pyridine ring, the dearomatized N of the pyridine ring, a “P”, a “T”, an NH, an imine nitrogen, or “Q” of the ligands described herein. The stereochemistry of “X” associated with the metal or metal ion “M” is not limited to a planar structure but is merely depicted this way for convenience.
- Selected structures include, for example, PN3P-pincer nickel (Ni) complexes 1 through 3, which are useful for dehydrogenation of formic acid are depicted below. Further details regarding different embodiments are provided throughout this disclosure.
- Phospho-Amino Pincer-Type Ligands
- In one aspect, the disclosure provides compounds of formulae (I) through (III) as well as the ligands for complexes noted throughout.
- Examples of such ligands and methods of preparing them, and optionally deprotonating them, are provided throughout this disclosure. For example, see He, L.-P.; Chen, T.; Gong, D.; Lai, Z.-P.; Huang, K.-W. Organometallics 2012, 31, 5208-5211. C2. Chen, T.; He, L.; Gong, D.; Yang, L.; Maio, X.; Eppinger, J.; Huang, K.-W. Tetrahedron Lett. 2012, 53, 4409-4412. C3. He, L.-P.; Chen, T.; Xue, D.; Eddaoudi, M.; Huang, K.-W. J. Organomet. Chem. 2012, 700, 202-206, the contents of which are incorporated herein in their entirety.
- These methods can be further modified and optimized using the principles and techniques of organic chemistry as applied by a person skilled in the art. Such principles and techniques are taught, for example, in March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (2007), which is incorporated by reference herein. The above methods can be further modified and optimized for preparative, pilot- or large-scale production, either batch of continuous, using the principles and techniques of process chemistry as applied by a person skilled in the art. Such principles and techniques are taught, for example, in Practical Process Research & Development (2000), which is incorporated by reference herein.
- Phospho-Amino, Pincer-Type Ligand Complexes and Methods of Use
- The present disclosure also provides metal complexes of this novel class of ligands. Such complexes may be used to facilitate a variety of organic transformations, including conversion of carbon dioxide to methanol, conversion of aldehydes into alcohols, conversion of aldehydes in the presence of a trifluoromethylation agent into trifluorinated secondary alcohols, cycloaddition of carbon dioxide to an epoxide to provide cyclic carbonates and preparation of an amide from the combination of an alcohol and an amine.
- For example, nickel complexes of ligands can be made, and optionally deprotonated, to provide a dearomatized pyridine moiety and an imine arm. Nickel complexes of
ligands 1, 2 and 3 can catalyze, for example, the conversion of aldehydes to alcohols (Tables 1 and 2) or carbon dioxide to methanol (Table 3). - The above methods can be further modified and optimized for preparative, pilot- or large-scale production, either batch of continuous, using the principles and techniques of process chemistry as applied by a person skilled in the art. Such principles and techniques are taught, for example, in Practical Process Research & Development (2000), which is incorporated by reference herein.
- Definitions
- When used in the context of a chemical group, “hydrogen” means —H; “hydroxy” means —OH; “oxo” means ═O; “halo” means independently —F, —Cl, —Br or —I; “amino” means —NH2 (see below for definitions of groups containing the term amino, e.g., alkylamino); “hydroxyamino” means —NHOH; “nitro” means —NO2; imino means ═NH (see below for definitions of groups containing the term imino, e.g., alkylimino); “cyano” means —CN; “isocyanate” means —N═C═O; “azido” means —N3; in a monovalent context “phosphate” means —OP(O)(OH)2 or a deprotonated form thereof; in a divalent context “phosphate” means —OP(O)(OH)O— or a deprotonated form thereof; “mercapto” means —SH; “thio” means ═S; “thioether” means —S—; “sulfonamido” means —NHS(O)2— (see below for definitions of groups containing the term sulfonamido, e.g., alkylsulfonamido); “sulfonyl” means —S(O)2—(see below for definitions of groups containing the term sulfonyl, e.g., alkylsulfonyl); and “sulfinyl” means —S(O)— (see below for definitions of groups containing the term sulfinyl, e.g., alkylsulfinyl).
- In the context of chemical formulas, the symbol “—” means a single bond, “═” means a double bond, and “≡” means triple bond. The symbol “----” represents an optional bond, which if present is either single or double. The symbol “” represents a single bond or a double bond. Thus, for example, the structure
- includes the structures
- As will be understood by a person of skill in the art, no one such ring atom forms part of more than one double bond. The symbol “”, when drawn perpendicularly across a bond indicates a point of attachment of the group. It is noted that the point of attachment is typically only identified in this manner for larger groups in order to assist the reader in rapidly and unambiguously identifying a point of attachment. The symbol “” means a single bond where the group attached to the thick end of the wedge is “out of the page.” The symbol “” means a single bond where the group attached to the thick end of the wedge is “into the page”. The symbol “” means a single bond where the conformation (e.g., either R or S) or the geometry is undefined (e.g., either E or Z).
- Any undefined valency on an atom of a structure shown in this application implicitly represents a hydrogen atom bonded to the atom. When a group “R” is depicted as a “floating group” on a ring system, for example, in the formula:
- then R may replace any hydrogen atom attached to any of the ring atoms, including a depicted, implied, or expressly defined hydrogen, so long as a stable structure is formed. When a group “R” is depicted as a “floating group” on a fused ring system, as for example in the formula:
- then R may replace any hydrogen attached to any of the ring atoms of either of the fused rings unless specified otherwise. Replaceable hydrogens include depicted hydrogens (e.g., the hydrogen attached to the nitrogen in the formula above), implied hydrogens (e.g., a hydrogen of the formula above that is not shown but understood to be present), expressly defined hydrogens, and optional hydrogens whose presence depends on the identity of a ring atom (e.g., a hydrogen attached to group X, when X equals —CH—), so long as a stable structure is formed. In the example depicted, R may reside on either the 5-membered or the 6-membered ring of the fused ring system. In the formula above, the subscript letter “y” immediately following the group “R” enclosed in parentheses, represents a numeric variable. Unless specified otherwise, this variable can be 0, 1, 2, or any integer greater than 2, only limited by the maximum number of replaceable hydrogen atoms of the ring or ring system.
- For the groups and classes below, the following parenthetical subscripts further define the group/class as follows: “(Cn)” defines the exact number (n) of carbon atoms in the group/class. “(C≦n)” defines the maximum number (n) of carbon atoms that can be in the group/class, with the minimum number as small as possible for the group in question, e.g., it is understood that the minimum number of carbon atoms in the group “alkenyl(C≦8)” or the class “alkene(C≦8)” is two. For example, “alkoxy(C≦10)” designates those alkoxy groups having from 1 to 10 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, or any range derivable therein (e.g., 3 to 10 carbon atoms). (Cn-n′) defines both the minimum (n) and maximum number (n′) of carbon atoms in the group. Similarly, “alkyl(C2-10)” designates those alkyl groups having from 2 to 10 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, or 10, or any range derivable therein (e.g., 3 to 10 carbon atoms)).
- The term “saturated” as used herein means the compound or group so modified has no carbon-carbon double and no carbon-carbon triple bonds, except as noted below. The term does not preclude carbon-heteroatom multiple bonds, for example a carbon oxygen double bond or a carbon nitrogen double bond. Moreover, it does not preclude a carbon-carbon double bond that may occur as part of keto-enol tautomerism or imine/enamine tautomerism.
- The term “aliphatic” when used without the “substituted” modifier signifies that the compound/group so modified is an acyclic or cyclic, but non-aromatic hydrocarbon compound or group. In aliphatic compounds/groups, the carbon atoms can be joined together in straight chains, branched chains, or non-aromatic rings (alicyclic). Aliphatic compounds/groups can be saturated, that is joined by single bonds (alkanes/alkyl), or unsaturated, with one or more double bonds (alkenes/alkenyl) or with one or more triple bonds (alkynes/alkynyl). When the term “aliphatic” is used without the “substituted” modifier only carbon and hydrogen atoms are present. When the term is used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —N(CH3)2, —C(O)NH2 or —OC(O)CH3.
- The term “alkyl” when used without the “substituted” modifier refers to a monovalent saturated aliphatic group with a carbon atom as the point of attachment, a linear or branched, cyclo, cyclic or acyclic structure, and no atoms other than carbon and hydrogen. Thus, as used herein cycloalkyl is a subset of alkyl. The groups —CH3 (Me), —CH2CH3 (Et), —CH2CH2CH3 (n-Pr), —CH(CH3)2 (iso-Pr), —CH(CH2)2 (cyclopropyl), —CH2CH2CH2CH3 (n-Bu), —CH(CH3)CH2CH3 (sec-butyl), —CH2CH(CH3)2 (iso-butyl), —C(CH3)3 (tert-butyl), —CH2C(CH3)3 (neo-pentyl), cyclobutyl, cyclopentyl, cyclohexyl, and cyclohexylmethyl are non-limiting examples of alkyl groups. The term “alkanediyl” when used without the “substituted” modifier refers to a divalent saturated aliphatic group, with one or two saturated carbon atom(s) as the point(s) of attachment, a linear or branched, cyclo, cyclic or acyclic structure, no carbon-carbon double or triple bonds, and no atoms other than carbon and hydrogen. The groups, —CH2— (methylene), —CH2CH2—, —CH2C(CH3)2CH2—, —CH2CH2CH2—, and
- are non-limiting examples of alkanediyl groups. The term “alkylidene” when used without the “substituted” modifier refers to the divalent group ═CRR′ in which R and R′ are independently hydrogen, alkyl, or R and R′ are taken together to represent an alkanediyl having at least two carbon atoms. Non-limiting examples of alkylidene groups include: ═CH2, ═CH(CH2CH3), and ═C(CH3)2. When any of these terms is used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, — C(O)CH3, —N(CH3)2, —C(O)NH2 or —OC(O)CH3. The following groups are non-limiting examples of substituted alkyl groups: —CH2OH, —CH2Cl, —CF3, —CH2CN, —CH2C(O)OH, —CH2C(O)OCH3, —CH2C(O)NH2, —CH2C(O)CH3, —CH2OCH3, —CH2OC(O)CH3, —CH2NH2, —CH2N(CH3)2, and —CH2CH2Cl. The term “fluoroalkyl” is a subset of substituted alkyl, in which one or more hydrogen has been substituted with a fluoro group and no other atoms aside from carbon, hydrogen and fluorine are present. The groups, —CH2F, —CF3, and —CH2CF3 are non-limiting examples of fluoroalkyl groups. An “alkane” refers to the compound H—R, wherein R is alkyl.
- The term “alkenyl” when used without the “substituted” modifier refers to an monovalent unsaturated aliphatic group with a carbon atom as the point of attachment, a linear or branched, cyclo, cyclic or acyclic structure, at least one nonaromatic carbon-carbon double bond, no carbon-carbon triple bonds, and no atoms other than carbon and hydrogen. Non-limiting examples of alkenyl groups include: —CH═CH2 (vinyl), —CH═CHCH3, —CH═CHCH2CH3, —CH2CH═CH2 (allyl), —CH2CH═CHCH3, and —CH═CH—C6H5. The term “alkenediyl” when used without the “substituted” modifier refers to a divalent unsaturated aliphatic group, with two carbon atoms as points of attachment, a linear or branched, cyclo, cyclic or acyclic structure, at least one nonaromatic carbon-carbon double bond, no carbon-carbon triple bonds, and no atoms other than carbon and hydrogen. The groups, —CH═CH—, —CH═C(CH3)CH2—, —CH═CHCH2—, and
- are non-limiting examples of alkenediyl groups. When these terms are used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —N(CH3)2, —C(O)NH2 or —OC(O)CH3. The groups, —CH═CHF, —CH═CHCl and —CH═CHBr, are non-limiting examples of substituted alkenyl groups. An “alkene” refers to the compound H—R, wherein R is alkenyl.
- The term “alkynyl” when used without the “substituted” modifier refers to an monovalent unsaturated aliphatic group with a carbon atom as the point of attachment, a linear or branched, cyclo, cyclic or acyclic structure, at least one carbon-carbon triple bond, and no atoms other than carbon and hydrogen. As used herein, the term alkynyl does not preclude the presence of one or more non-aromatic carbon-carbon double bonds. The groups, —C≡CH, —C≡CCH3, and —CH2C≡CCH3, are non-limiting examples of alkynyl groups. The term “alkynediyl” when used without the “substituted” modifier refers to a divalent unsaturated aliphatic group, with two carbon atoms as points of attachment, a linear or branched, cyclo, cyclic or acyclic structure, at least one carbon-carbon triple bond, and no atoms other than carbon and hydrogen. When these terms are used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —N(CH3)2, —C(O)NH2 or —OC(O)CH3. An “alkyne” refers to the compound H—R, wherein R is alkynyl.
- The term “aryl” when used without the “substituted” modifier refers to a monovalent unsaturated aromatic group with an aromatic carbon atom as the point of attachment, said carbon atom forming part of a one or more six-membered aromatic ring structure, wherein the ring atoms are all carbon, and wherein the group consists of no atoms other than carbon and hydrogen. If more than one ring is present, the rings may be fused or not fused. As used herein, the term does not preclude the presence of one or more alkyl group (carbon number limitation permitting) attached to the first aromatic ring or any additional aromatic ring present. Non-limiting examples of aryl groups include phenyl (Ph), methylphenyl, (dimethyl)phenyl, —C6H4CH2CH3 (ethylphenyl), naphthyl, and the monovalent group derived from biphenyl. The term “arenediyl” when used without the “substituted” modifier refers to a divalent aromatic group, with two aromatic carbon atoms as points of attachment, said carbon atoms forming part of one or more six-membered aromatic ring structure(s) wherein the ring atoms are all carbon, and wherein the monovalent group consists of no atoms other than carbon and hydrogen. As used herein, the term does not preclude the presence of one or more alkyl group (carbon number limitation permitting) attached to the first aromatic ring or any additional aromatic ring present. If more than one ring is present, the rings may be fused or unfused. Non-limiting examples of arenediyl groups include:
- When these terms are used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —N(CH3)2, —C(O)NH2 or —OC(O)CH3. An “arene” refers to the compound H—R, wherein R is aryl.
- The term “aralkyl” when used without the “substituted” modifier refers to the monovalent group -alkanediyl-aryl, in which the terms alkanediyl and aryl are each used in a manner consistent with the definitions provided above. Non-limiting examples of aralkyls are: phenylmethyl (benzyl, Bn) and 2-phenyl-ethyl. When the term is used with the “substituted” modifier one or more hydrogen atom from the alkanediyl and/or the aryl has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —N(CH3)2, —C(O)NH2 or —OC(O)CH3. Non-limiting examples of substituted aralkyls are: (3-chlorophenyl)-methyl, and 2-chloro-2-phenyl-eth-1-yl.
- The term “heteroaryl” when used without the “substituted” modifier refers to a monovalent aromatic group with an aromatic carbon atom or nitrogen atom as the point of attachment, said carbon atom or nitrogen atom forming part of an aromatic ring structure wherein at least one of the ring atoms is nitrogen, oxygen or sulfur, and wherein the group consists of no atoms other than carbon, hydrogen, aromatic nitrogen, aromatic oxygen and aromatic sulfur. As used herein, the term does not preclude the presence of one or more alkyl group (carbon number limitation permitting) attached to the aromatic ring or any additional aromatic ring present. Non-limiting examples of heteroaryl groups include furanyl, imidazolyl, indolyl, indazolyl (Im), methylpyridyl, oxazolyl, pyridyl, pyrrolyl, pyrimidyl, pyrazinyl, quinolyl, quinazolyl, quinoxalinyl, thienyl, and triazinyl. The term “heteroarenediyl” when used without the “substituted” modifier refers to an divalent aromatic group, with two aromatic carbon atoms, two aromatic nitrogen atoms, or one aromatic carbon atom and one aromatic nitrogen atom as the two points of attachment, said atoms forming part of one or more aromatic ring structure(s) wherein at least one of the ring atoms is nitrogen, oxygen or sulfur, and wherein the divalent group consists of no atoms other than carbon, hydrogen, aromatic nitrogen, aromatic oxygen and aromatic sulfur. As used herein, the term does not preclude the presence of one or more alkyl group (carbon number limitation permitting) attached to the first aromatic ring or any additional aromatic ring present. If more than one ring is present, the rings may be fused or unfused. Non-limiting examples of heteroarenediyl groups include:
- When these terms are used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —N(CH3)2, —C(O)NH2 or —OC(O)CH3.
- The term “acyl” when used without the “substituted” modifier refers to the group —C(O)R, in which R is a hydrogen, alkyl, aryl, aralkyl or heteroaryl, as those terms are defined above. The groups, —CHO, —C(O)CH3 (acetyl, Ac), —C(O)CH2CH3, —C(O)CH2CH2CH3, —C(O)CH(CH3)2, —C(O)CH(CH2)2, C(O)C6H5, C(O)C6H4CH3, C(O)CH2C6H5, —C(O)(imidazolyl) are non-limiting examples of acyl groups. A “thioacyl” is defined in an analogous manner, except that the oxygen atom of the group —C(O)R has been replaced with a sulfur atom, —C(S)R. When either of these terms are used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —N(CH3)2, —C(O)NH2 or —OC(O)CH3. The groups, —C(O)CH2CF3, —CO2H (carboxyl), —CO2CH3 (methylcarboxyl), —CO2CH2CH3, —C(O)NH2 (carbamoyl), and —CON(CH3)2, are non-limiting examples of substituted acyl groups.
- The term “alkoxy” when used without the “substituted” modifier refers to the group —OR, in which R is an alkyl, as that term is defined above. Non-limiting examples of alkoxy groups include: —OCH3, —OCH2CH3, —OCH2CH2CH3, —OCH(CH3)2, —OCH(CH2)2, —O-cyclopentyl, and —O-cyclohexyl. The terms “alkenyloxy”, “alkynyloxy”, “aryloxy”, “aralkoxy”, “heteroaryloxy”, and “acyloxy”, when used without the “substituted” modifier, refers to groups, defined as —OR, in which R is alkenyl, alkynyl, aryl, aralkyl, heteroaryl, and acyl, respectively. Similarly, the term “alkylthio” when used without the “substituted” modifier refers to the group —SR, in which R is an alkyl, as that term is defined above. When any of these terms is used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —N(CH3)2, —C(O)NH2 or —OC(O)CH3. The term “alcohol” corresponds to an alkane, as defined above, wherein at least one of the hydrogen atoms has been replaced with a hydroxy group.
- The term “alkylamino” when used without the “substituted” modifier refers to the group —NHR, in which R is an alkyl, as that term is defined above. Non-limiting examples of alkylamino groups include: —NHCH3 and —NHCH2CH3. The term “dialkylamino” when used without the “substituted” modifier refers to the group —NRR′, in which R and R′ can be the same or different alkyl groups, or R and R′ can be taken together to represent an alkanediyl. Non-limiting examples of dialkylamino groups include: —N(CH3)2, —N(CH3)(CH2CH3), and N-pyrrolidinyl. The terms “alkoxyamino”, “alkenylamino”, “alkynylamino”, “arylamino”, “aralkylamino”, “heteroarylamino”, and “alkylsulfonylamino” when used without the “substituted” modifier, refers to groups, defined as —NHR, in which R is alkoxy, alkenyl, alkynyl, aryl, aralkyl, heteroaryl, and alkylsulfonyl, respectively. A non-limiting example of an arylamino group is —NHC6H5. The term “amido” (acylamino), when used without the “substituted” modifier, refers to the group —NHR, in which R is acyl, as that term is defined above. A non-limiting example of an amido group is —NHC(O)CH3. The term “alkylimino” when used without the “substituted” modifier refers to the divalent group ═NR, in which R is an alkyl, as that term is defined above. When any of these terms is used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —N(CH3)2, —C(O)NH2 or —OC(O)CH3. The groups —NHC(O)OCH3 and —NHC(O)NHCH3 are non-limiting examples of substituted amido groups.
- The above definitions supersede any conflicting definition in any of the reference that is incorporated by reference herein. The fact that certain terms are defined, however, should not be considered as indicative that any term that is undefined is indefinite. Rather, all terms used are believed to describe the invention in terms such that one of ordinary skill can appreciate the scope and practice the present invention.
- In the specification and in the claims, the terms “including” and “comprising” are open-ended terms and should be interpreted to mean “including, but not limited to . . . .” These terms encompass the more restrictive terms “consisting essentially of” and “consisting of.”
- It must be noted that as used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural reference unless the context clearly dictates otherwise. As well, the terms “a” (or “an”), “one or more” and “at least one” can be used interchangeably herein. It is also to be noted that the terms “comprising”, “including”, “characterized by” and “having” can be used interchangeably.
- Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs. All publications and patents specifically mentioned herein are incorporated by reference in their entirety for all purposes including describing and disclosing the chemicals, instruments, statistical analyses and methodologies which are reported in the publications which might be used in connection with the invention. All references cited in this specification are to be taken as indicative of the level of skill in the art. Nothing herein is to be construed as an admission that the invention is not entitled to antedate such disclosure by virtue of prior invention.
- The following paragraphs enumerated consecutively from 1 through 30 provide for various aspects of the embodiments described herein. In one embodiment, in a first paragraph (1), the present invention provides a complex comprising a ligand and a metal or metal ion, M, wherein the ligand is a compound according to formula (I), or a deprotonated version thereof, and the ligand is associated with the metal or metal ion, M,
- wherein R1 and R2, are each independently alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- R3, and R4, if present, are each independently alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- R5 is a hydrogen atom or an alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- each Z, independently, is CR6, N or P;
- R6 is a hydrogen atom or an alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- T is a N, NR7, CR8, or CR9R10;
- R7, R8, R9 and R10 are each independently a hydrogen, alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- Q is P or N;
- optionally, wherein T and Q, together, form a 5 or 6 membered heterocyclic ring; wherein the heterocyclic ring can optionally be substituted with one or more heteroatoms and or one or more sites of the heterocyclic ring are substituted with one or more alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups, and optionally wherein the heterocyclic ring can have a fused ring attached thereto, provided when T and Q form a 5 or 6 membered heterocyclic ring, R3 and R4 are not present;
-
- M is nickel (Ni), a nickel ion or a nickel salt; and
- X is a halide or a hydrogen atom associated with M or the complex.
- 2. The composition of paragraph 1, wherein R1, R2, R3, and R4 are each a alkyl(C2-10), each Z is CH, T is N or NR7 and R5 is a hydrogen atom.
- 3. The composition of paragraph 2, wherein R1, R2, R3, and R4 are each a C4 alkyl and T is NR7.
- 4. The composition of any of paragraphs 1 through 3, wherein R7 is a methyl group or a hydrogen.
- 5. The composition of any of paragraphs 1 through 4, wherein X is a hydrogen atom (a hydride).
- 6. The compound of any of paragraphs 1 through 4, wherein X is a halide.
- 7. A compound comprising formula (II):
- wherein R1, R2, R3, and R4 are each independently alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- R5 is a hydrogen atom or an alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- each Z, independently, is CR6, N or P;
- R6 is a hydrogen atom or an alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- D is NR7 or CR9R10; in one aspect, D is NR7.
- R7, R9 and R10 are each independently a hydrogen, alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- M is a nickel (Ni) or a nickel ion or salt; and
- X is a halide or a hydrogen atom.
- 8. The compound of paragraph 7, wherein R1, R2, R3, and R4 are each a alkyl(C2-10), each Z is CH and R5 is a hydrogen atom.
- 9. The compound of paragraph 8, wherein R1, R2, R3, and R4 are each a C4 alkyl.
- 10. The compound of any of paragraphs 7 through 9, wherein R7 is a methyl group or a hydrogen.
- 11. The compound of any of paragraphs 7 through 10, wherein X is a hydrogen atom (a hydride).
- 12. The compound of any of paragraphs 7 through 10, wherein X is a halide.
- 13. A composition comprising formula (III):
- wherein R1, R2, R3, and R4 are each independently alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- R5 is a hydrogen atom or an alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- each Z, independently, is CR6, N or P;
- R6 is a hydrogen atom or an alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- R7 is a hydrogen, alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups;
- M is nickel (Ni), a nickel ion or a nickel salt;
- X is a halide or a hydrogen atom; and
- a base.
- 14. The composition of paragraph 13, wherein R1, R2, R3, and R4 are each a alkyl(C2-10), each Z is CH and R5 is a hydrogen atom.
- 15. The composition of paragraph 14, wherein R1, R2, R3, and R4 are each a C4 alkyl.
- 16. The composition of any of paragraphs 13 through 15, wherein R7 is a methyl group or a hydrogen.
- 17. The composition of any of paragraphs 13 through 16, wherein X is a hydrogen atom (a hydride).
- 18. The composition of any of paragraphs 13 through 18, wherein X is a halide.
- 19. The composition of any of paragraphs 13 through 18, wherein the base is an organic base.
- 20. The composition of paragraph 19, wherein the organic base is an amine or an alkoxide.
- 21. The composition of paragraph 20, wherein the amine is an alkylamine comprising NR20R21R23, wherein R20, R21 and R23 are each independently a hydrogen atom, alkyl(C≦12), aryl(C≦12), aralkyl(C≦12), or a substituted version of any of these groups, wherein one or more of R20, R21 and R22 can form a ring or an aromatic amine.
- 22. The composition of paragraph 21, wherein the aromatic amine is pyridine.
- 23. A method to prepare methanol from carbon dioxide comprising the step:
- contacting carbon dioxide and a silane with the compound or composition of any of paragraphs 1 through 22 to form a mixture, wherein the carbon dioxide is converted to methanol.
- 24. The method of paragraph 23, wherein the silane is diphenyl silane.
- 25. The method of either paragraphs 23 or 24, further comprising the step of treating mixture with an aqueous base.
- 26. A method to prepare alcohols from an aldehyde comprising the step:
- contacting an aldehyde and a silane with the compound or composition of any of paragraphs 1 through 22 to form a mixture, wherein the aldehyde is converted to an alcohol.
- 27. The method of paragraph 26, further comprising the step of treating mixture with an aqueous base.
- 28. A method to trifluoromethylate an aldehyde comprising the step:
- contacting an aldehyde with trifluoromethyltrimethylsilane with the compound or composition of any of paragraphs 1 through 22 to form a mixture, wherein the aldehyde is converted to a trifluoromethyl alcohol product.
- 29. A method to prepare cyclic carbonates from an alkyl or aryl epoxide and carbon dioxide, comprising the step:
- contacting an alkyl or aryl epoxide with carbon dioxide with the compound or composition of any of paragraphs 1 through 22, wherein the alkyl or aryl epoxide is converted into a cyclic carbonate.
- 30 A method to prepare an amide from an alcohol and an amine comprising the step:
- contacting a primary alkyl alcohol or an aryl group containing a primary alcohol and a primary or secondary alkyl or aryl amine with a compound or composition of any of paragraphs 1 through 22 in the presence of a ruthenium catalyst, including ruthenium metal salts, wherein the alcohol and amine are converted into an amide.
- The most direct synthesis of thee complexes starts with the reaction of the known ligand A and a nickel(II) halide source. Accordingly, complex B was obtained by heating NiCl2 with ligand A in toluene, a similar procedure to that of its bromide analog by Kirchner.22,23 The following t-BuOK deprotonation afforded the dearomatized pincer nickel complex 1. The preparation of Ni—H complex 2 was achieved by oxidative addition of A to bis(1,5-cyclooctadiene)nickel(0) in toluene (Scheme 6). Upon treatment with t-BuOK and methyl iodide in toluene, complex 2 was methylated to afford pincer Ni—
H complex 3. - The reaction of benzaldehyde 4a and phenylsilane 5 was investigated in the presence of various pincer nickel complexes (1.0 mol %) and benzyl alcohol was obtained in 99% yield when 2 was employed (Table 1, entry 1). Slightly lower yields of benzyl alcohol were observed when
complexes 1 and 3 were tested with longer reaction time (Table 1, entries 2 and 3). No product was observed without using Ni complexes (Table 1, entry 4). These observations suggested that complexes 1-3 serve as the catalyst and 2 was the best among them. Reaction screenings with various solvents (Table 1, entries 5-7), under different temperatures and catalyst loadings (Table 1, entries 8-11) indicated that 0.2 mol % of 2 showed satisfactory catalyst performance in toluene at 80° C. -
TABLE 1 Optimization of the reaction conditions in the hydrosilylation of aldehyde 4a catalyzed by nickel PN3P-Pincer Hydride Complexes.[a] yield (%)[b] Entry Cat. x T (° C.) Solvent t (h) 6a 1 2 1.0 80 toluene 16 99 2 3 1.0 80 toluene 24 94 3 1 1.0 80 toluene 48 93 4 none — r.t toluene 24 0 5 2 1.0 40 DCM 48 75 6 2 1.0 70 THF 48 83 7 2 1.0 80 CH3CN 48 75 8 2 1.0 r.t toluene 24 10 9 2 0.5 80 toluene 16 99 10 2 0.2 80 toluene 16 99 11 2 0.1 80 toluene 24 88 [a]The reaction was carried out on a 0.4-mmol scale, and the ratio of 4a/5 was 1.0/0.4. [b]Isolated yield after basic work-up. - The scope of this catalytic system was then studied and the reduction products were isolated as alcohols after basic hydrolysis of the resulting silyl ethers.
Benzaldehyde 4 bearing either electron-rich or electron-poor functional groups could all react smoothly to give the correspondingalcohols 6 in excellent yields (Table 2). Trans-cinnamaldehyde was converted to cinnamyl alcohol selectively at 60° C. and no sign of 1,4-reduction was detected (Table 2, entry 11), in sharp contrast to the results of similar reactions catalyzed by pincer Ni—H24 or carbene-Cu—H complexes.25 Hydrosilylation of a mixture of acetophenone (1.0 equiv.) and benzaldehyde (1.0 equiv.) catalyzed by 2 gave benzyl alcohol 6a in quantitative yield with full recovery of acetophenone, revealing the excellent chemoselectivity towards the aldehyde substrates (Scheme 3). -
TABLE 2 Substrate scope of hydrosilylation of aldehyde 4 with 5 catalyzed by 2.[a]Isolated yield (%)[b] Entry[a] R 6 1 4a, X = H 6a, 99 2 4b, X = 4-Me 6b, 90 3 4c, X = 3-Me 6c, 85 4 4d, X = 2-MeO 6d, 93 5 4e, X = 4-Cl 6e, 90 6 4f, X = 4-Br 6f, 96 7 4g, X = 2-CF3 6g, 86 8 4h, X = 2-OH 6h, 91 9 4i, 2-pyridyl 6i, 94 10 6j, 83 11 6k, 85[c] [a]Unless otherwise specified, all reactions were performed on a 1-mmol scale in dry toluene (1 mL) under Ar in the presence of 2 (0.2 mol %) at 80° C. [b]Isolated yields after basic work-up. [c]the reaction was performed at 60° C. for 48 h. - Reduction of CO2 was examined with compound 2. It was found that methanol was obtained in 91% yield upon basic hydrolysis workup with 1.25 mol % of 2. This result is similar to that of the hydrosilylation of CO2 catalyzed by N-heterocyclic carbenes reported by Zhang and Ying,14 but in sharp contrast to those of the reactions catalyzed by metal hydrides, where CH4 was identified as the final product.26,27 Scheme 9.
- Using tertiary amines, such as Et3N and DABCO (1,4-Diazabicyclo[2.2.2]octane) and imine, such as DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) as the catalysts led to no methanol product (Table 3, entries 4-6). The reaction worked well in polar aprotic solvents such as DMF, THF, and MeCN, with slower reaction rates in THF and MeCN (Table 3, entries 7 and 8), presumably because DMF can act as a Lewis base to help to activate silane and thus accelerate the reaction.28 No reaction was observed in CH2Cl2 and toluene (Table 3, entries 9 and 10). Further screening of catalyst loadings (Table 3, entries 11-16) revealed that diphenylsilane could be fully consumed with a catalyst loading as low as 0.02 mol % (Table 3, entry 16). The turnover number (TON) and turnover frequency (TOF) for hydride 2 as the catalyst in this reaction could reach 4900 and 136 h−1, respectively (Table 3, entry 16), much higher than those of the (N-heterocyclic carbene) NHC catalysts.14 To the best of our knowledge, this is the highest TON and TOF reported for the reduction of CO2 with silane to methanol.
-
TABLE 3 The reaction conditions screening for hydrosilylation of CO2 with diphenylsilane catalyzed by nickel PN3P-pincer complexes.[a] Catalyst loading Entry Catayst [mol % Si—H] Solvent t [h][b] Yield [%][c] 1 2 1.25 DMF 12 91 2 3 1.25 DMF 20 85 3 1 1.25 DMF 48 88 4 Et3N 1.25 DMF 48 0 5 DABCO 1.25 DMF 48 0 6 DBU 1.25 DMF 48 0 7 2 1.25 THF 24 90 8 2 1.25 MeCN 36 91 9 2 1.25 CH2Cl2 —[d] — 10 2 1.25 toluene —[d] — 11 2 5.00 DMF 6 91 12 2 2.50 DMF 8 91 13 2 0.50 DMF 16 92 14 2 0.25 DMF 24 90 15 2 0.05 DMF 28 87 16 2 0.02[e] DMF 36 98 [a]Reaction conditions: CO2 balloon, catalyst, 1.0 mmol of diphenylsilane, 1.0 mL of solvent, and the reaction was carried out at rt-60° C. [b]Time required for the full consumption of diphenylsilane monitored by GC/MS. [c]Yields of methanol determined by GC. [d]Nearly no reaction. [e]2.0 mmol of diphenylsilane was used. - While the conventional wisdom is to modify the reactivities and selectivities of the coordination metal catalysts and organocatalysts through changing the steric and/or electronic properties of organic substituent groups, it is demonstrated herein that the reactivity of the organic imine group could be increased through coordinating to the Ni metal center and changing the spectator ligand on Ni. When the chloride ligand on the Ni center in 1 was replaced with a hydride in 2, the nucleophilicity of the imine N atom was significantly enhanced such that this imine group achieves an improved activity than those of NHCs in nucleophilic covalent bonding activation for the hydrosilylation of carbonyl compounds, the first catalytic activity of its kind for imine groups.
- Synthesis of 1: To a suspension of 1,3-(tBu2PNH)2C6H4 (1.0 g, 4.0 mmol) in toluene (20 ml) was added anhydrous NiCl2 (519 mg, 4.0 mmol) under an argon atmosphere, giving an orange suspension. While the solution was being boiled for 18 h, a brown precipitate formed, which was removed by filtration after the mixture was cooled to room temperature. The volume of the orange filtrate was reduced to 5 mL, and then pentane was added to cause precipitation. The product was collected by filtration, washed with pentane (3×3 mL), and dried under vacuum to give an orange powder of complex B (1.96 g, 86% yield). To a THF (5 mL) suspension of B (45 mg, 0.091 mmol) was added tBuOK (11.2 mg, 0.095 mmol), resulting in a color change from yellowish to brown. The solvent was removed under vacuum, and the complex was extracted with benzene. Solvent evaporation yielded complex 1 (40 mg, 90% yield) as an brown solid. IR (neat, cm−1): ν=3350 (NH); 1H NMR (400 MHz, (CD3)2SO): δ 7.44 (s, 1H), 6.81 (dd, J=8.8, 7.2 Hz, 1H), 5.74 (d, J=8.8, 1H), 5.43 (d, J=7.2 Hz, 1H), 1.38-1.45 (m, 36H); 13C NMR ((CD3)2SO, 100 MHz): δ 173.1 (d, J=10.3 Hz), 162.6 (dd, J=11.2, 8.6 Hz), 138.6, 101.6 (d, J=21.5 Hz), 88.1 (d, J=7.7 Hz), 38.1 (d, J=5.2 Hz), 37.9 (d, J=5.2 Hz), 37.4 (d, J=2.5 Hz), 37.3 (d, J=2.6 Hz), 27.93, 27.91, 27.65, 27.60; 31P NMR (162 MHz, (CD3)2SO): δ 59.3 (d, J=285.4 Hz, 1P), 40.1 (d, J=285.4 Hz, 1P); HRMS (ESI) Calcd. for C21H41ClN3NiP2 requires (M+H+) 490.1818, Found: 490.1796; Elemental analysis (%) for C21H40ClN3NiP2: Calc. C, 51.41; H, 8.22; N, 8.56. Found: C, 51.59; H, 8.10; N, 8.41.
- Synthesis of 2: To a suspension of 1,3-(tBu2PNH)2C6H4 (1.0 g, 4.0 mmol) in toluene (20 ml) was added Ni(COD)2 (220 mg, 0.8 mmol) under an argon atmosphere, and the mixture was stirred and heated at 80° C. for 12 h, then cooled to room temperature. The pale yellow solid 2 thus obtained was filtered and washed with pentane (3×3 mL), then dried under vacuum (1.5 g, 85%). IR (neat, cm−1): ν=1866 (Ni—H), 3353 (NH); 1H NMR (400 MHz, C6D6): δ 6.95 (t, J=7.2 Hz, 1H), 6.71 (s, 1H), 5.22 (s, 1H), 4.03 (s, 1H), 1.49 (s, 18H), 1.04 (s, 18H), −15.9 (t, J=56.0 Hz, 1H); 13C NMR (DMF-d7, 100 MHz): δ 172.9 (dd, J=9.5, 4.7 Hz), 138.6, 128.8, 102.8 (d, J=25.0 Hz), 87.4 (d, J=9.5 Hz), 36.5, 36.3, 28.5; 31P NMR (162 MHz, C6D6): δ 82.7 (d, J=217.1 Hz, 1P), 74.8 (d, J=217.1 Hz, 1P); HRMS (ESI) Calcd. for C21H42N3NiP2 requires (M+H+) 456.2207, Found: 456.2201. Elemental analysis (%) for C21H41N3NiP2: Calc. C, 55.29; H, 9.06; N, 9.21. Found: C, 55.21; H, 8.96; N, 9.02.
- Synthesis of 3: To a solution of 2 (1.0 g, 2.2 mmol) in toluene (22 mL) were added KOtBu (494 mg, 4.4 mmol) and MeI (625 mg, 0.28 mL, 4 mmol). The mixture was refluxed for 12 h, which was filtered after the mixture was cooled to room temperature. The volume of the orange filtrate was reduced to 5 mL, and then pentane was added to cause precipitation. The product was collected by filtration, washed with pentane (3 ×3 mL), and dried under vacuum to give an yellow powder of 3 (722 mg, 70% yield). IR (neat, cm−1): ν=1871 (Ni—H); 1H NMR (400 MHz, C6D6): δ 7.01 (t, J=7.2 Hz, 1H), 6.80 (d, J=7.2, 1H), 5.04 (d, J=7.2 Hz, 1H), 2.55 (s, 3H), 1.51 (s, 9H), 1.48 (s, 9H), 1.18 (s, 9H), 1.15 (s, 9H), −15.6 (dd, J=60.8, 45.6 Hz, 1H); 13C NMR (C6D6, 100 MHz): δ 173.2 (dd, J=9.5, 3.5 Hz), 161.7 (dd, J=13.8, 6.9 Hz), 138.1, 106.9 (d, J=21.5 Hz), 86.0 (d, J=7.7 Hz), 38.1 (d, J=1.7 Hz), 38.0 (d, J=1.7 Hz), 36.6 (d, J=4.3 Hz), 36.4 (d, J=5.2 Hz), 36.3, 30.1, 30.0, 29.0, 28.9; 31P NMR (162 MHz, C6D6): δ 91.8 (dd, J=224.9, 17.7 Hz, 1P), 83.9 (dd, J=224.9, 25.3 Hz, 1P); HRMS (ESI) Calcd. for C22H43N3NiP2 requires (M+H+) 470.2364, Found: 470.2338; Elemental analysis (%) for C22H42N3NiP2: Calc. C, 56.19; H, 9.22; N, 8.94. Found: C, 56.26; H, 9.21; N, 8.91.
- General procedures for hydrosilylation of aldehyde: to a flame-dried Schlenk flask was added a solution of nickel PN3P-pincer complex 2 (1.0 mg, 2 μmol) in toluene (1.0 mL), an aldehyde substrate (1.0 mmol) and PhSiH3 (49 μL, 0.4 mmol) under an argon atmosphere. The resulting mixture was stirred at 80° C. until there was no aldehyde left (monitored by withdrawing aliquots and analyzing their 1H NMR spectra). The reaction was then quenched by a 10% aqueous solution of NaOH (about 1.0 mL) with vigorous stirring for more than 12 hours. The solution containing the alcohol product was extracted with diethyl ether three times, dried over anhydrous Na2SO4, and concentrated under vacuum. The desired alcohol was further purified by flash column chromatography.
- General procedures for reduction of CO2 to methanol: to a fresh vial was added nickel PN3P-pincer complex 2 (4.6 mg, 0.01 mmol), and 1.8 mL of DMF was introduced. The vial was sealed, and CO2 was introduced into the vial via a balloon. The reaction was allowed to stir for 30 min at room temperature, after which diphenylsilane (0.19 mL, 1 mmol) was introduced. The reaction was quenched after 18 h by adding 2 equivalents of NaOH/H2O solution. It was stirred for another 24 h before an aliquot of isopropyl alcohol was added as an internal standard. An aliquot of 0.2 mL was removed from the sample and diluted with dichloromethane before the resulting mixture was subjected to GC analysis.
- General procedure for trifluoromethylation of benzaldehyde: to benzaldehyde (0.11 g, 1.0 mmol) in a dry flask under Ar were added DMF (anhydrous, 1 mL), TMSCF3 (0.4 g, 2.8 mmol), and nickel PN3P-pincer complex 2 (9.1 mg, 0.02 mmol). The mixture was stirred at room temperature for 5 h. HCl solution (2N, 1 mL) was added and the solution was stirred at room temperature until all TMS protected intermediate converted to product. Water (6 mL) was added and aqueous layer was extracted with ether (4 mL×3). Organic layers were combined and washed with saturated NaHCO3 aqueous solution (3 mL), brine (3 mL), dried over MgSO4. Solvents were removed under vacuum to the crude residue, which was purified by silica flash chromatography (30% ethyl actate/hexanes) to give 149 mg product (85% yield).
- General procedure for cycloaddition of CO2 to epoxide: a mixture of the styrene oxide (0.5 mL, 4.4 mmol) and the nickel PN3P-pincer complex 2 (0.09 mmol, 41 mg) was charged in a dry flask; then CO2 was introduced (1 bar) and the mixture was heated at 100° C. for 48 h. The reaction mixture was then cooled to room temperature, methylene chloride was added and the product was purified over silica gel column (20% ethyl actate/hexanes).
- General procedure for amide synthesis from alcohols and amines: in an argon-filled glovebox, a 10 mL oven-dried Schlenk tube was charged with nickel PN3P-pincer complex 2 (0.025 mmol, 11 mg), KOtBu (0.075 mmol, 8.4 mg), and 0.6 mL of toluene. The Schlenk tube was then taken out, and benzylalcohol (0.50 mmol, 54 mg) and benzylamine (0.55 mmol, 59 mg) were added. The reaction mixture was heated to reflux under a flow of argon to facilitate removal of hydrogen for 24 hours before being cooled to room temperature. All the volatiles were removed under vacuum. Purification of the crude product by flash chromatography afforded amide, which was identified by spectral comparison with literature data.
- Generally the ligands and complexes can be prepared by the methods described in U.S. patent Ser. No. 13/528,481, filed on Jun. 6, 2012, entitled “Phospho-amino Pincer-Type Ligands and Catalytic Metal Complexes Thereof”, U.S. Provisional Patent Application No. 61/499,028, filed Jun. 20, 2011, and “Efficient transfer hydrogenation reaction Catalyzed by a dearomatized PN3P ruthenium pincer complex under base-free Conditions”, Journal of Organometallic Chemistry, 700 (2012) 202-206, “A sustainable catalytic pyrrole synthesis”, Nature Chemistry Vol. 5, 2013, 140-144 and Z. anorg. allg. Chem. 545 (1987) 83-97, the contents of which are incorporated herein by reference in their entirety.
- Although the present invention has been described with reference to preferred embodiments, persons skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. All references cited throughout the specification, including those in the background, are incorporated herein in their entirety. Those skilled in the art will recognize, or be able to ascertain, using no more than routine experimentation, many equivalents to specific embodiments of the invention described specifically herein. Such equivalents are intended to be encompassed in the scope of the following claims.
- The following references to the extent that they provide exemplary procedural or other details supplementary to those set forth herein, are specifically incorporated herein by reference.
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